Process for producing oxidized hydrocarbons and product thereof



' ,ra'ocsss roa Unsaturated hydrocarbonsusually the property of absorbing molecular oxygen; The

in consistency,'color,. reactivity, etc., depending on the nature of the unsaturated hydrocarbons PATENT.

V. ,raopUcm G oxmrznp mr- .nnocsnnoss rnonucr manor 4 Hyman, Chicago, 111., assignor to Velsicol Ill a corporation of November 1a. 1933, No. 698.590

v e 6 Claims. (cl. zoo-2i This-invention relates to improvements in the e manuiacture of oxidized hydrocarbons.

temperatures varying from about 1000. E. to about 1400 F., may be employed.

Oxidation should be carried out at as low a tem- Iperature as is economically feasible, in order. to

products resulting from such oxidation wfll vary prior to oxidation. Numerous and different types of oxidized hydroc r on have been reported in the literature.

The present invention has'to do with oxidized hydrocarbon mixtures which diiIer from other such mixtures bothin the nature oithe starting material and in therefrom.

when petroleum is subjected to vapor phase cracking (that is cracking at temperatures in excess of 1000 'F., and at pr never more than four or live times atmospheric) there results a cracked distillate relativelyrich in unsaturated the oxidized product resulting compounds. It has'been found that, when the gasoline portion 0! this distillate is carefully distilled; the first portion of said distillate is colorless. Asthe distillation proceeds,'the color of the distillate becomes progressively a deeper yellow. It. now, the more volatile fractions, (that is. the colorless or very pale colored fractions) are subjected to oxidation by molecular oxygen attemperatures not to exceed 175 1"., there'results a heavy oxidized polymer of an oleoreeinous na-' ture which. shows but very little ,tenden'cyto harden. This oleoresin, whose color is dependent on the temperature of oxidation as well as the color oi the starting material, has been round to mix readily with nitrocellulose solutions. and acta as an excellent plasticiser ior nitrocellulose. and

The raw material for the production or the oxidized hydrocarbons \oi invention. consists oil-the lighteriraction o! vapor phase crackedgasoline havingacoiornotyellowerthan 0. +18 Saybolt, although the more colorlees the raw material,thepalerwillbetheresulting oxi- ,disedhydrocarbonaotherthin'gsbeingequal.

preserve, insofar as possible, the paleness oi the g oxidized hydrocarbon. The oxidizing should not exceed about 175 F., although. normal atmospheric temperatures are, in general, to be preferred. The oxidation may be speeded up in a number of ways. Increase in temperature and/or in pressure will speed up oxidation. The greater the partial pressure of the oxygen used, the more rapid will be 'the oxidation. The. addition tothe gasoline fraction of soluble siccative metalcompounds, such as soaps of cobalt, manganese, etc., will help 5 greatly to increase the speed or oxidation. It should not be necessary to add more than onetenth of L% by weight of the gasoline i'raction to iii I have found thatthe. more volatile fractions 1 the distillate are for the manufac- .tu're oi'this Thus I preier a distillate which, when distilled'inthe ordimrylngisr-apparatus,'wllldistill at leastgiiq'b material before a vapor temperature of 230' I".,'will have Diflerent temperatures of V 90 will prodiwe distillates oi diil'ering- While..i n general, petroleum cracked at, about 1200 I be treated of the siccative metal in soap combina-' tion, although more or less than this amount may a. be used if desired. Any combination oil-the above mentioned methods for hastening oxidation'may be mployed.

The oxidation described above leaves the major portion 0! the gasoline unchanged. 2

After the oxidation has been carried on for a period of time sumcient to produce the desired quantity of oleoresin', the remaining gasoline may be removed either by evaporation or distillation. The latter operation may best be accomplished o inavacuumorunderareducedpartialpressure as, for example;'by means of a steam distillation.

The temperature oi the oleoresin during evapduring or distillation; it possible, the

temperature should be kept'below 175 1'. The

1 meredgasoline may beused as a motor. fuel,

'10: other required purpose. Asa rule, 40'

willnotbe I toremov'ealltheunoxidistillate from the oleoresin. mus the oi'theoleoresinmayheiurtherprotected.

order to prevent 'or retard a iurther'oxida ti .0! the-produced 'o leoresin, there may be it mixed withlt small quantities of antioxidants,

suchashydroquinon ,pyrbcatechimpara-aminophenol, phenylene diamine. alpha naphthol, alpha naphthylamme, maleic acid-etc. It should never beneeessarytoaddmorethaiioqttheweightot 50 'oleoresinas'antioxidant. althoiish moremay be addedii'desirable'oriicompatible. Usually, 1%

or less of antioxidant will be-iound quite'sufl-i cient. Iidesired, thesiccative metal may be treatment with very dilute acids, 'or by the addition to the oleoresin or oleoresin solution of a water soluble organic acid, such as acetic acid. Such an acid tends to convert the metals present to salts of this acid, which are water soluble and may be removed by washing.

An interesting property of the oxidized resin whose preparation isherein contemplated is that, when heated or baked, it readily turns brown. At

the same time, a condensation takes place, with the result that the oleoresin becomes less and less soluble in organic solvents, until finally it assumes what appears to be an insoluble and infusible state. This circumstance suggests the possibility of its use in the preparation of highly resistant baked coatings and impregnants.

I claim as my invention:

1. A process for producing oxidized hydrocarbons which comprises adding to a fraction of gasoline cracked in the vapor phase at temperatures between 1000 and 1400 F. and pressures below 5 atmospheres, at least of such fraction boiling below a temperature of 230 F. and having a color not yellower than +16 Saybolt, a siccative metal drier; subjecting said mixture to the action of molecular oxygen at a temperature below F.; and recovering a. heavy oxidized polymer of an oleoresinous nature.

2. A process for producing oxidized hydrocarbons which comprises subjecting a fraction of gasoline cracked in the vapor phase at temperatures between 1000 and 1400" F. and pressures below 5 atmospheres, at least 90% of such fraction boiling below 230 F. and having a color not yellower than +16 Saybolt, to superatmospheric pressure in the presence of molecular oxygen at a temperature below 175 F., and recovering an oxidized polymer of an oleoresinous nature.

3. An oxidized hydrocarbon oi oleoresinous nature derived from a fraction of gasoline cracked in the vapor phase at temperatures between 1000- 4. A plasticizer comprising an oxidized hydrocarbon of oleoresinous nature derived from a fraction of gasoline cracked in the vapor phase at temperatures between 1000 and 1400" F. and pressures below 5 atmospheres, at least 90% of such fraction boiling below 230 F. and having a color not yellower than +16 Saybolt, said fraction having been subjected to the action of molecular oxygen at temperatures below 175 F.

5. A baking varnish comprising an oxidized hydrocarbon of oleoresinous nature derived from a fraction of gasoline cracked in the vapor phase at temperatures between 1000 and 1400 F. and pressures below 5 atmospherea'at least 90% of such fraction boiling below 230 F. and having a color not yellower than +16 Saybolt, said fraction having been subjected to the action of molecular oxygen at temperatures below 175 F.

6. A mixture comprising a relatively small quantity of an antioxidant and an oxidized hydrocarbon of oleoresinous nature derived from a fraction of gasoline cracked in the vapor phase at temperatures between 1000 and 1400" F. and

. pressures below 5 atmospheres, at least 90% of such fraction boiling below 230 F. and having a color not yellower than +16 Saybolt, said fraction having been subjected to the action of molecular oxygen at temperatures below 175 F.

JULIUS HYMAN.

Gil 

